阅读说明：本技术 一种环保型防腐涂料及其制备方法 (Environment-friendly anticorrosive paint and preparation method thereof ) 是由 罗洪财 于 2019-09-16 设计创作，主要内容包括：本发明公开了一种环保型防腐涂料,包括如下重量份的各组分：钛基不饱和聚合物乳液45-55份、含硅丙烯酸单体26-32份、引发剂16-18份、乙醇65-70份、增稠剂2-3份、缓释填料6-7份、消泡剂1-2份、流平剂1-2份。该涂料以钛基不饱和聚合物乳液为反应单体与含硅丙烯酸单体直接反应制备基体树脂,由于钛基不饱和聚合物中的每个单体中均含有Ti-O键,使得制备的钛基不饱和聚合物中含有大量的Ti-O键,在与含硅单体聚合后生成的产物中含有大量的Ti-O键和硅烷键,进而使得制备的具体树脂本身就具有较高的疏水性能和耐污性能,并且无需另外添加纳米二氧化钛。(The invention discloses an environment-friendly anticorrosive paint which comprises the following components in parts by weight: 45-55 parts of titanium-based unsaturated polymer emulsion, 26-32 parts of silicon-containing acrylic acid monomer, 16-18 parts of initiator, 65-70 parts of ethanol, 2-3 parts of thickener, 6-7 parts of slow release filler, 1-2 parts of defoamer and 1-2 parts of flatting agent. The coating takes titanium-based unsaturated polymer emulsion as a reaction monomer to directly react with a silicon-containing acrylic acid monomer to prepare matrix resin, and each monomer in the titanium-based unsaturated polymer contains Ti-O bonds, so that the prepared titanium-based unsaturated polymer contains a large amount of Ti-O bonds, and a product generated after the titanium-based unsaturated polymer and the silicon-containing monomer are polymerized contains a large amount of Ti-O bonds and silane bonds, so that the prepared specific resin has high hydrophobic property and stain resistance, and no additional nano titanium dioxide is required to be added.)

1. The environment-friendly anticorrosive paint is characterized by comprising the following components in parts by weight:

45-55 parts of titanium-based unsaturated polymer emulsion, 26-32 parts of silicon-containing acrylic acid monomer, 16-18 parts of initiator, 65-70 parts of ethanol, 2-3 parts of thickener, 6-7 parts of slow release filler, 1-2 parts of defoamer and 1-2 parts of flatting agent;

the specific preparation process of the titanium-based unsaturated polymer emulsion comprises the following steps:

step 1: adding the mixed solvent into a reaction kettle, heating to 90-95 ℃ for reflux, then adding tetrabutyl titanate and triethanolamine into the reaction vessel, carrying out reflux reaction for 10-12h under the constant temperature condition, and then evaporating to remove the solvent to obtain a powder product;

step 2: adding the powder product prepared in the step 1 into ether, stirring and dissolving, heating to 230-240 ℃, refluxing, adding p-toluenesulfonic acid, stirring and reacting for 10-15min, adding maleic anhydride, and refluxing at constant temperature for 10-12 h;

and step 3: and adding the product into a high-speed shearing emulsification tank, simultaneously adding polyoxyethylene sorbitan fatty acid ester and SP-80 into the high-speed shearing emulsification tank, and performing high-speed shearing emulsification for 1-2h to obtain the titanium-based unsaturated polymer emulsion.

2. The environment-friendly anticorrosive paint as claimed in claim 1, wherein the silicon-containing acrylic monomer is one of allyltrimethoxysilane or allyltriethoxysilane.

3. The environment-friendly anticorrosive paint according to claim 1, wherein the initiator is one of benzoyl peroxide, azobisisobutyronitrile and ammonium persulfate.

4. The environment-friendly anticorrosive paint as claimed in claim 1, wherein the mixed solvent in the step 1 is glycerol and isopropanol in a mass ratio of 1: 0.5, while adding tetrabutyl titanate in an amount of 30g per 100mL of the mixed solvent, and the ratio of tetrabutyl titanate to triethanolamine by mass is 1: 2 are mixed and added.

5. The environment-friendly anticorrosive paint as claimed in claim 1, wherein in step 2, 12-13mL of diethyl ether, 0.21-0.23g of p-toluenesulfonic acid and 0.92-0.93g of powder product are added to each gram of maleic anhydride.

6. The environment-friendly anticorrosive paint as claimed in claim 1, wherein the volume ratio of polyoxyethylene sorbitan fatty acid ester to SP-80 in step 3 is 1: 0.82-0.83, and the volume ratio of the polyoxyethylene sorbitan fatty acid ester to the ether solution is 0.15-0.16: 1.

7. the environment-friendly anticorrosive paint as claimed in claim 1, wherein the slow-release filler is prepared by the following specific steps: adding zinc acetate dihydrate and absolute ethyl alcohol into a reaction container at the same time, heating to 50-55 ℃, carrying out reflux reaction for 40-50min, adding the obtained product into a beaker, adding dried diatomite into the beaker, carrying out ultrasonic dispersion uniformly, adding lithium hydroxide into the beaker, carrying out ultrasonic reaction for 30-40min, filtering, heating the obtained solid to 450 ℃ at the speed of 5 ℃/min in a muffle furnace, and roasting for 30-32h to obtain the slow-release filler.

8. The environment-friendly anticorrosive paint as claimed in claim 7, wherein each gram of zinc acetate dihydrate is added with 30-35mL of absolute ethanol, 0.13-0.14g of lithium hydroxide and 4-4.2g of diatomite.

9. The environment-friendly anticorrosive coating as claimed in claim 1, wherein the environment-friendly anticorrosive coating is prepared by the following specific steps: adding the titanium-based unsaturated polymer emulsion and ethanol into a reaction vessel simultaneously, introducing nitrogen into the reaction vessel for 20-30min, adding an initiator into the reaction vessel, uniformly mixing, heating to 80-90 ℃, dropwise adding a silicon-containing acrylic monomer into the reaction vessel, reacting for 1-1.5h after complete dropwise addition, heating to 120-130 ℃, stirring for 2-3h, cooling to room temperature, discharging the obtained product solution, pouring the product solution into a stirring kettle, sequentially adding a slow release filler, a leveling agent, a defoaming agent and a thickening agent into the stirring kettle, and mixing and stirring for 20-30min to obtain the environment-friendly anticorrosive paint.

Technical Field

The invention belongs to the field of paint preparation, and relates to an environment-friendly anticorrosive paint and a preparation method thereof.

Background

In the life, a large amount of resources and energy are wasted due to metal corrosion, in order to reduce the corrosion of metal materials, a layer of anticorrosive paint is usually coated on the surface of metal, and the anticorrosive performance is realized through the action of the paint, in the existing anticorrosive paint preparation process, nano-fillers such as nano-titanium dioxide are usually added into matrix resin to realize the anticorrosive performance, but the nano-fillers are easy to agglomerate to reduce the nano-effect, and the nano-fillers are directly and completely exposed in the coating and are easy to be rapidly reacted and deteriorated in the environment of stronger acid-base salt, so that the anticorrosive performance and other performances of the prepared paint are rapidly reduced or disappeared.

Disclosure of Invention

The invention aims to provide an environment-friendly anticorrosive paint and a preparation method thereof, the paint takes titanium-based unsaturated polymer emulsion as a reaction monomer to directly react with a silicon-containing acrylic monomer to prepare matrix resin, each monomer in the titanium-based unsaturated polymer contains Ti-O bonds, so that the prepared titanium-based unsaturated polymer contains a large amount of Ti-O bonds, and a product generated after the titanium-based unsaturated polymer is polymerized with the silicon-containing monomer contains a large amount of Ti-O bonds and silane bonds, so that the prepared specific resin has higher hydrophobic property and stain resistance, and no nano titanium dioxide is required to be additionally added, thereby effectively solving the problems that the nano fillers such as nano titanium dioxide are usually added into the matrix resin in the preparation process of the existing anticorrosive paint to realize the anticorrosive property, but the nano fillers are easy to agglomerate to cause the reduction of the nano effect, thereby causing a problem of deterioration of corrosion prevention and stain resistance.

And because the titanium-based unsaturated polymer is a hyperbranched structure, the prepared resin has a hyperbranched structure, wherein the slow-release filler can be uniformly dispersed in the coating, when the nano zinc dioxide released by the slow-release filler can be uniformly dispersed in the filler, the polymerization of the nano zinc dioxide is reduced, meanwhile, the slow-release filler added in the coating can slowly release the nano zinc dioxide, so that the nano zinc dioxide is uniformly distributed in the coating on the surface of the workpiece all the time, the nano zinc dioxide is uniformly dispersed and can not agglomerate, and even if the released nano zinc dioxide is deformed in reaction, the filler can still continuously release the nano zinc dioxide, so that the coating has a higher impedance value all the time and is in a corrosion-resistant state all the time

The purpose of the invention can be realized by the following technical scheme:

an environment-friendly anticorrosive paint comprises the following components in parts by weight:

45-55 parts of titanium-based unsaturated polymer emulsion, 26-32 parts of silicon-containing acrylic acid monomer, 16-18 parts of initiator, 65-70 parts of ethanol, 2-3 parts of thickener, 6-7 parts of slow release filler, 1-2 parts of defoamer and 1-2 parts of flatting agent;

the silicon-containing acrylic monomer is one of allyl trimethoxy silane or allyl triethoxy silane;

the initiator is one of benzoyl peroxide, azobisisobutyronitrile and ammonium persulfate;

the specific preparation process of the titanium-based unsaturated polymer emulsion comprises the following steps:

step 1: adding a mixed solvent into a reaction kettle, heating to 90-95 ℃ for reflux, then adding tetrabutyl titanate and triethanolamine into the reaction vessel, carrying out reflux reaction for 10-12h under a constant temperature condition, and then evaporating to remove the solvent to obtain a powder product, wherein the mixed solvent is glycerol and isopropanol according to a mass ratio of 1: 0.5, while adding tetrabutyl titanate in an amount of 30g per 100mL of the mixed solvent, and the ratio of tetrabutyl titanate to triethanolamine by mass is 1: 2, mixing and adding; because the outermost layer of the titanium ions has empty orbitals, and the nitrogen atoms in the triethanolamine can provide lone-pair electrons, so that the nitrogen atoms are used as ligands and can be complexed with the titanium ions, two triethanolamine are introduced into the prepared product, and then six alcoholic hydroxyl groups are introduced into the product and are in different directions;

step 2: adding the powder product prepared in the step 1 into ether, stirring and dissolving, heating to 230-240 ℃, refluxing, adding p-toluenesulfonic acid, stirring and reacting for 10-15min, adding maleic anhydride, and refluxing at constant temperature for 10-12 h; wherein 12-13mL of ether is added into each gram of maleic anhydride, 0.21-0.23g of p-toluenesulfonic acid is added, and 0.92-0.93g of powder product is added; the acid anhydride group in the maleic anhydride can react with the alcoholic hydroxyl group in the powder product, and the powder product contains the alcoholic hydroxyl group in six different directions, so that the powder product can be polymerized with the maleic anhydride in six different directions to generate the hyperbranched polymer; each monomer in the polymer contains Ti-O bonds, so that the prepared polymer contains a large amount of Ti-O bonds, and the hydrophobicity and the stain resistance of the polymer are improved;

and step 3: adding the product into a high-speed shearing emulsification tank, simultaneously adding polyoxyethylene sorbitan fatty acid ester and SP-80 into the high-speed shearing emulsification tank, and performing high-speed shearing emulsification for 1-2h to obtain a titanium-based unsaturated polymer emulsion; wherein the volume ratio of the polyoxyethylene sorbitan fatty acid ester to the SP-80 is 1: 0.82-0.83, and the volume ratio of the polyoxyethylene sorbitan fatty acid ester to the ether solution is 0.15-0.16: 1;

the preparation process of the slow-release filler is as follows: adding zinc acetate dihydrate and absolute ethyl alcohol into a reaction container at the same time, heating to 50-55 ℃, performing reflux reaction for 40-50min, adding the obtained product into a beaker, adding dried diatomite into the beaker, performing ultrasonic dispersion uniformly, adding lithium hydroxide into the beaker, performing ultrasonic reaction for 30-40min, filtering, heating the obtained solid to 450 ℃ at the speed of 5 ℃/min in a muffle furnace, and roasting for 30-32h to obtain a slow-release filler; wherein, 30 to 35mL of absolute ethyl alcohol is added into zinc acetate dihydrate per gram, 0.13 to 0.14g of lithium hydroxide is added, and 4 to 4.2g of diatomite is added; because the diatomite contains a large number of pore channel structures, under the ultrasonic action, a mixture solution of zinc acetate and absolute ethyl alcohol enters the pore channels of the diatomite, reacts with lithium hydroxide in the pore channels to generate gel, and is roasted at high temperature to generate nano zinc oxide which is loaded inside the pore channels of the diatomite; after the coating is coated, the outer coating layer has higher waterproof performance, can effectively prevent moisture from contacting the surface of the coated workpiece, simultaneously slowly releases nano zinc dioxide by slowly releasing the filler, the nano zinc dioxide has higher impedance value, can realize higher corrosion resistance, but is easy to agglomerate, the impedance value of the agglomerated workpiece is reduced, further the corrosion resistance of the agglomerated workpiece is reduced, and the nano zinc dioxide can react or agglomerate when the workpiece is soaked for a long time or is in an environment with higher pH value for a long time, further the impedance value of the workpiece is reduced, the corrosion resistance is reduced, but the nano zinc dioxide is uniformly distributed in the coating on the surface of the workpiece all the time by slowly releasing the nano zinc dioxide, the dispersion is uniform, the agglomeration cannot occur, and the filler can continuously release the nano zinc dioxide even if the released nano zinc dioxide is deformed by reaction, the coating has a high impedance value all the time and is in a corrosion-resistant state all the time;

the specific preparation process of the environment-friendly anticorrosive paint is as follows:

adding the titanium-based unsaturated polymer emulsion and ethanol into a reaction vessel simultaneously, introducing nitrogen into the reaction vessel for 20-30min, adding an initiator into the reaction vessel, uniformly mixing, heating to 80-90 ℃, dropwise adding a silicon-containing acrylic monomer into the reaction vessel, reacting for 1-1.5h after complete dropwise addition, heating to 120-130 ℃, stirring for 2-3h, cooling to room temperature, discharging the obtained product solution, pouring the product solution into a stirring kettle, sequentially adding a slow release filler, a leveling agent, a defoaming agent and a thickening agent into the stirring kettle, and mixing and stirring for 20-30min to obtain the environment-friendly anticorrosive paint; the titanium-based unsaturated polymer emulsion contains unsaturated olefin groups, and the silicon-containing acrylic monomer also contains olefin groups, and free radical polymerization reaction is carried out under the action of an initiator to generate a polymer, the generated polymer contains a large number of Ti-O bonds, so that the hydrophobicity and the stain resistance of the coating are improved, the coating has self-cleaning effect after being coated on the surface of a workpiece, the number of times of wiping the workpiece by using an organic solvent is reduced, the environmental protection performance is realized, and a large number of siloxane bonds are introduced into the coating, so that the hydrophobicity of the coating is improved, the high heat resistance of the coating is realized, the outer layer of the prepared coating has high waterproof performance, and when an external waterproof layer is damaged, the nano zinc dioxide released by the inner layer has a high impedance value, and the corrosion resistance of the coating is further improved; meanwhile, because the titanium-based unsaturated polymer is of a branched structure, the titanium-based unsaturated polymer can be well and uniformly dispersed with the silicon-containing acrylic monomer, and the load is uniform, so that the content of siloxane bonds in the prepared coating is uniform, and the thermal stability of the coating is uniform.

The invention has the beneficial effects that:

1. the coating prepared by the invention takes the titanium-based unsaturated polymer emulsion as a reaction monomer to directly react with the silicon-containing acrylic acid monomer to prepare matrix resin, because each monomer in the titanium-based unsaturated polymer contains Ti-O bonds, the prepared titanium-based unsaturated polymer contains a large amount of Ti-O bonds, the product generated after the polymerization with the silicon-containing monomer contains a large amount of Ti-O bonds and silane bonds, further, the prepared specific resin has higher hydrophobic property and stain resistance without adding nano titanium dioxide, effectively solves the problem that nano fillers such as nano titanium dioxide are usually added into matrix resin in the preparation process of the prior anticorrosive coating to realize the anticorrosive property, but the nano-filler is easy to agglomerate to cause the reduction of the nano effect, thereby causing the reduction of the corrosion resistance and the pollution resistance.

2. The titanium-based unsaturated polymer prepared by the invention is of a hyperbranched structure, so that the prepared resin has the hyperbranched structure, the slow-release filler added in the coating can be uniformly dispersed in the coating, when the nano zinc dioxide released by the slow-release filler can be uniformly dispersed in the filler, the polymerization of the nano zinc dioxide is reduced, meanwhile, the slow-release filler added in the coating can slowly release the nano zinc dioxide, the nano zinc dioxide is uniformly distributed in the coating on the surface of a workpiece all the time, the nano zinc dioxide is uniformly dispersed and can not agglomerate, and even if the released nano zinc dioxide is deformed by reaction, the filler can continuously release the nano zinc dioxide, so that the coating has a higher impedance value all the time and is in a corrosion-resistant state all the time, thereby solving the problem that the nano fillers such as nano titanium dioxide and the like are usually added in the matrix resin in the preparation process of the existing anticorrosive, the nano filler is directly and completely exposed in the coating, and is easy to be rapidly reacted and deteriorated in the environment with stronger acid-base salt, so that the corrosion resistance and other properties of the prepared coating are rapidly reduced or disappeared.

Detailed Description